If the production of reformulated gasolines is to meet the new environmental standards, it is necessary, in particular, to reduce the concentration of olefins slightly and the concentration of aromatics (especially benzene) and sulphur to a large degree. Gasolines produced by catalytic cracking, which may account for 30 to 50% of the gasoline pool, have high contents of olefins and sulphur. In about 90% of cases, the sulphur present in reformulated gasolines is attributable to gasoline produced by catalytic cracking (FCCxe2x80x94Fluid Catalytic Cracking, or catalytic cracking operated in a fluidized bed). Desulphurization (hydro-desulphirization) of gasolines and of FCC gasolines in particular is therefore becoming manifestly more important as a means of meeting specifications. Apart from gasoline produced by catalytic cracking, other gasolines, such as gasolines obtained directly from the distillation of crude oil, or gasolines produced by conversion (coking, steam cracking or others) may account for a significant contribution to the sulphur in gasoline.
Hydro-cracking (hydro-desulphurization) of the feedstock introduced in catalytic cracking gives rise to gasolines which typically contain 100 ppm of sulphur. However, the units used for hydro-processing feedstocks in catalytic cracking are operated under severe temperature and pressure conditions, implying a high capital outlay. Furthermore, the entire feedstock used in the catalytic cracking process has to be desulphurized, which means having to process very high volumes of feedstock.
When conducted under the conventional conditions with which the skilled person is familiar, hydro-processing (hydro-desulphurization) of gasolines from catalytic cracking enables the sulphur content of the cut to be reduced. However, this process has the major disadvantage of leading to a very high drop in the octane number of the cut due to the fact that a significant proportion of the olefins becomes saturated during hydro-processing.
The idea of separating the light gasoline from the heavy gasoline prior to hydro-processing has already been claimed by patent U.S. Pat. No. 4,397,739. This type of separation enables a light cut, rich in olefins and with a low sulphur content, which will no longer be compatible with future specifications, to be separated from a rich heavy cut with a low olefin content and containing a high proportion of the sulphur from the initial gasoline. This patent claims a process of hydro-desulphurizing gasolines, which consists in fractionating the gasoline into a light fraction and a heavy fraction followed by specific hydro-desulphurization of the heavy gasoline but does not propose any solution for eliminating the sulphur present in the light gasoline.
U.S. Pat. No. 4,131,537, on the other hand, teaches a process based on fractionating the gasoline into several cuts, preferably three, depending on their boiling point, and desulphurizing them under conditions which may be different and in the presence of a catalyst containing at least one metal from group VIB and/or group VII. According to this patent, the main benefit is to be obtained by fractionating the gasoline into three cuts and treating the cut having intermediate boiling points under mild conditions.
Patent application EP-A-0 725 126 describes a process of desulphurizing a gasoline derived from cracking in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds that can be readily desulphurized and a second fraction rich in compounds that are difficult to desulphurize. Prior to this separation, it is necessary to determine the distribution of products containing sulphur by analyses. These analyses are necessary in order to select the equipment and the separation conditions.
This application states, for example, that the olefin content and octane number of a light fraction of gasoline derived from cracking will drop significantly if it is desulphurized without being fractionated. Fractionating said light fraction into 7 to 20 fractions, on the other hand, followed by analysis of the sulphur and olefin contents of these fractions enables the fractions with the highest contents of sulphur compounds to be determined and these are then desulphurized simultaneously or separately and mixed with the other desulphurized fractions or not. A procedure of this type is complex and has to be reproduced with each change in the composition of the gasoline to be treated.
French patent application No. 98/14480 teaches the idea of fractionating the gasoline into a light fraction and a heavy fraction, followed by a specific hydro-treatment of the light gasoline on a nickel-based catalyst and a hydro-treatment of the heavy gasoline on a catalyst containing at least one metal from group VIII and/or at least one metal from group VIb.
Processes for hydro-treating gasolines have also been proposed, in patent U.S. Pat. No. 5,290,427 for example, which consist in fractionating the gasoline, then delivering the fractions to different levels of a hydro-desulphurization reactor and converting the (desulphurized fractions on a ZSM-5 zeolite in order to compensate for the detected loss of octane by isomerization.
In these processes, the gasolines to be treated generally have an initial point in excess of 70xc2x0 C. and again, it is necessary to treat the light gasoline (fraction corresponding to the compounds with a boiling point between the C5 (hydrocarbons with 5 carbon atoms) and 70xc2x0 C. separately by softening.
U.S. Pat. No. 5,318,690 proposes a process which consists in fractionating the gasoline and softening the light gasoline, whilst the heavy gasoline is desulphurized and then converted on ZSM-5 and desulphurized again under soft conditions. This technique is based on separating the crude gasoline to obtain a light cut which contains practically no sulphur compounds other than mercaptans. This enables said cut to be treated by a softening process only, which removes the mercaptans.
As a result, the heavy gasoline contains a relatively high quantity of olefins, which are partially saturated during hydro-processing. In order to compensate for the loss in octane number inherent in hydrogenation of the olefins, the patent proposes cracking on a ZSM-5 zeolite, which produces olefins but to the detriment of yield. Furthermore, these olefins may recombine with the H2S present in the medium to reform mercaptans. It is therefore necessary to operate a softening process or additional hydro-desulphurization.
The present invention relates to a process of desulphurizing gasoline, i.e. a process of producing gasolines with a low sulphur content, which enables an entire feedstock containing the sulphur (generally a gasoline cut) to be processed, preferably a gasoline cut produced by catalytic cracking, and allows the sulphur content in said gasoline cut to be reduced to very low levels, without significantly reducing the gasoline yield and whilst minimising the drop in octane number due to hydrogenation of the olefins. The process according to the invention also enables at least some of the potential octane losses caused by hydrogenation of the olefins to be restored by reforming one of the previously desulphurized gasoline fractions.
The process according to the invention is a process of producing gasoline with a low sulphur content from a feedstock containing sulphur. It comprises at least the following steps:
a1) at least one selective hydrogenation of the diolefins and acetylene compounds present in the feedstock,
a2) optionally at least one step intended to increase the molecular weight of the light sulphur products present in the feedstock or the effluent from step a1. This step may optionally be performed simultaneously with step al for at least a part of the feedstock, in the same reactor or a different reactor. It may also be operated separately on at least some of the feedstock hydrogenated at step a1.
b) at least one separation (also referred to as fractionation hereafter) of the gasoline obtained at step a1 or a2 into at least three fractions (or cuts), a light fraction containing the lightest olefins from the initial gasoline (light gasoline or light fraction), a heavy fraction in which the greater part of the sulphur compounds initially present in the original gasoline is concentrated (heavy gasoline or fraction) and at least one intermediate fraction with a relatively low olefin content and aromatic content and hence a low octane number compared with the light and heavy fractions of this gasoline.
c1) at least one treatment of the heavy gasoline separated at step b on a catalyst, enabling the unsaturated sulphur compounds to be at least partially decomposed or hydrogenated, in particular the cyclic sulphur or even aromatic compounds such as the thiophenic compounds for example, by operating under conditions conducive to limiting hydrogenation of the olefins on this catalyst. Prior to or after this step c1, the heavy fraction may optionally be mixed with at least a part of an intermediate fraction from the separation step b and preferably not desulphurized.
c2) step c1 is optionally followed by a step c2 of processing the effluent from step c1 on a catalyst, which enables the sulphur compounds and more preferably the linear and/or cyclic saturated sulphur compounds, to be decomposed, accompanied by limited hydrogenation of the olefins.
d) at least one step intended to reduce significantly the sulphur and nitrogen content of at least one of the intermediate fractions. This step of removing the sulphur and nitrogen is preferably accompanied by a practically total hydrogenation of the olefins contained in this fraction. The resultant fraction is then preferably treated by catalytic reforming in order to increase the octane number of said intermediate cut(s).
e) and optionally a step e during which at least two fractions are mixed, one of which, at least, having been subjected to a desulphurization treatment at step c1 and optionally c2 and/or at step d.
The catalytic treatments at steps c1 and/or c2 may be operated either in a single reactor containing the two catalysts or in at least two different reactors. If the treatment is operated using two reactors, they are preferably disposed in series, the second reactor preferably being used to treat all the effluent issuing from the first reactor, preferably without separating the liquid and gas between the first and second reactor. It is also possible to use several reactors, disposed in parallel or in series, for one and/or the other of steps c1 or c2.
Furthermore, a step e is preferably operated after step d, this step consisting in mixing the gasolines separated at step b, whether they have been subjected to desulphurization treatments or not.
The feedstock used in the process according to the invention is generally a gasoline cut containing sulphur, such as a cut from a coking, visbreaking, steam cracking or catalytic cracking (FCC) unit, for example. Said feedstock preferably consists of a gasoline cut from a catalytic cracking unit, in which the range of boiling points typically ranges from approximately the boiling points of hydrocarbons with 5 carbon atoms (C5) up to approximately 250xc2x0 C. This gasoline may optionally contain a significant fraction of gasoline from origins other than the gasolines derived directly from atmospheric distillation of crude oil (straight run gasoline) or a conversion process (coked or steam cracked gasoline, for example). The final point of the gasoline cut will depend on the refinery from which it came as well as market constraints, but is generally within the limits given above.
The present invention describes a process of producing a gasoline containing sulphur compounds, preferably from a catalytic cracking unit, in which the gasoline is firstly subjected to a selective hydrogenation treatment of the olefins and acetylenic compounds, optionally followed by a step intended to make heavier the lightest sulphur compounds which may be present in the gasoline and would otherwise be present in the light gasoline after fractionation if this step were omitted, at least one process of separating the gasoline into at least three fractions, treatment of at least one of the intermediate fractions with a view to removing most of the sulphur and nitrogen from this cut before applying a catalytic reforming treatment, treatment of the heavy gasoline, optionally mixed with at least a part of one of the intermediate fractions, using a known catalyst, in order to promote transformation of the unsaturated sulphur compounds present in the gasoline, such as the thiophenic compounds for example, into saturated sulphur compounds such as thiophane or mercaptans, optionally followed by a second catalyst to promote selective transformation of the saturated sulphur compounds, linear or cyclic, already present in the heavy cut or produced during the previous treatment. The heavy and intermediate fractions thus treated and optionally the light gasoline fraction may then be mixed in order to obtain a desulphurized gasoline.
This process chain enables a desulphurized gasoline to be obtained in fine, allowing the content of olefins or octane index to be controlled and does so al high desulphurization rates. This process enables high hydro-desulphurization rates to be obtained under reasonable operating conditions, as will be described below. Furthermore, by optimising the cut points of intermediate fractions and selecting those to be directed to the catalytic reforming step, the benzene content in the final gasoline can be reduced to a minimum (for example to contents of less than 5% by weight in the final mixture of desulphurized gasoline fractions), the olefin content can be controlled and the values of the Research Octane Number and Motor Octane Number can be kept high.
The sulphur species contained in the feedstocks treated by the process of the invention may be mercaptans or heterocyclic compounds such as thiophens or alkyl-thiophens, for example, or heavier compounds such as benzothiophen or dibenzothiophen. If a gasoline containing light sulphur compounds is fractionated into two cuts, a light cut rich in olefins and a heavy cut with a low olefin content, the light sulphur compounds (for example ethyl mercaptan, propyl mercaptan and optionally thiophen) may be partially or even totally present in the light gasoline. This being the case, it is often necessary to apply an additional treatment to this light fraction in order to reduce its sulphur content. Conventionally, this treatment takes the form of an extractive softening process which enables the light sulphur compounds present in the form of mercaptans to be removed from the gasoline. Apart from the fact that this treatment increases the cost of the operation prohibitively, it is only feasible if the sulphur is in the form of mercaptan. Accordingly, the fractionation point of the gasoline must preferably be limited so as not to give rise to the presence of thiophen in the light gasoline. The latter, in effect, forms azeotropes with a certain number of hydrocarbons so that only the C5 olefins and a small proportion of the C6 olefins can be separated from the light gasoline without giving rise to too large a fraction of thiophen in this cut.
In the process according to the invention, in order to recover a larger fraction of the olefins present in the light gasoline whilst limiting the sulphur content of this fraction without additional treatment, it is proposed, as a preference, that the feedstock be treated, after a first selective hydrogenation step, under conditions and on catalysts which enable the light sulphur compounds to be converted into sulphur compounds with a higher boiling point so that they will be contained in the heavier fractions after the separation step. The gasoline is then fractionated into at least three cuts: a light fraction which contains a significant fraction of the olefins initially present in the gasoline to be treated but a low quantity of sulphur compounds, at least one intermediate fraction from which the sulphur and nitrogen have been removed prior to treatment on a reforming catalyst, and a heavy fraction which is desulphurized under defined conditions and using a catalyst or a chain of catalysts enabling high desulphurization rates to be obtained whilst limiting the hydrogenation rate of the olefins and hence the loss of octane.
In order to minimise the benzene content of the final gasoline, one of the preferred approaches to implementing the invention is to treat the feedstock under conditions and using catalysts which enable the light sulphur compounds to be transformed into sulphur compounds with higher boiling points which will then be found in the heavier fractions after the separation step. The gasoline is then separated into 4 cuts:
a light fraction containing the main fraction of molecules with 5 carbon atoms (C5) and a significant fraction of the molecules with 6 carbon atoms (C6) initially present in the gasoline to be treated. This fraction is characterised by a high concentration of olefins and a very low sulphur content.
a first intermediate fraction essentially (i.e. more than 60% by weight and preferably more than 80% by weight) consisting of molecules with six carbon atoms (C6) and a part of the molecules having 7 carbon atoms (C7) as well as the greater part of sulphur compounds with a boiling point close to that of the azeotrope which it forms with the hydrocarbons, give or take approximately 20%. This fraction is preferably mixed with the heavy gasoline prior to hydro-desulphurization (steps c1 and c2) or after at least partial decomposition or hydrogenation of the unsaturated sulphur compounds (step c1) but before decomposition of the saturated sulphur compounds (step c2), so that it can be desulphurized under conditions that will enable hydrogenation of the olefins to be limited. By preference, this gasoline is not delivered to the catalytic reforming process because it contains a number of compounds which would cause benzene to form during the reforming treatment. The person skilled in the art is familiar with these compounds as xe2x80x9cbenzene precursorsxe2x80x9d, which may be methyl cyclopentane, n-hexane or benzene itself, for example. If permitted under local legislation, however, this intermediate cut may optionally be fed to the unit processing the second intermediate cut;
a second intermediate fraction from which sulphur and nitrogen have been removed on a conventional hydro-treatment catalyst in order to eliminate virtually all the sulphur and nitrogen initially present in this cut (i.e. to reduce their content to less than 5 ppm, preferably less than 1 ppm). This treatment is accompanied by virtually total hydrogenation of the olefins in this cut, enabling the olefin content to be reduced to values preferably below 10% by weight and even more preferably below 5% by weight. This cut is then treated on a catalytic reforming catalyst enabling isomerization and dehydrocyclization of the paraffins and naphthenes with formation of branched paraffins and aromatic compounds.
the heavy cut, preferably mixed with the first intermediate fraction, is desulphurized under defined conditions and using a chain of catalysts enabling high desulphurization rates to be obtained whilst limiting the rate of hydrogenation of the olefins and hence the loss in octane.
Accordingly, when the light, intermediate and heavy gasoline cuts are mixed after the desulphurization treatments proposed by the invention, the drop in Research or Motor Octane Number, expressed as the difference between the mean value (RON+MON)/2 observed in this mixture and the mean value (RON+MON)/2 of the initial feedstock, is limited to less than 2 points of octane, preferably less than 1.7 points of octane, and even more preferably less than 1.5 points of octane, and yet more preferably less than 1 point o octane. In certain cases, the mean value (RON+MON)/2 of the gasoline desulphurized by the process according to the invention may fall by less than 0.5 point octane relative to the mean value (RON+MON)/2 of the feedstock, or, on the contrary, may even increase by at least 0.5 point.
The sulphur content of gasoline cuts produced by catalytic cracking (FCC) depends on the sulphur content of the feedstock treated by FCC and on the final point of the cut. Generally speaking, the sulphur content of a gasoline cut as a whole, in particular those resulting from FCC, are greater than 100 ppm by weight and more often than not greater than 500 ppm by weight. In gasoline cuts whose final points are higher than 200xc2x0 C., the sulphur content is often greater than 1000 ppm by-weight and in certain cases may even be as much as 4000 to 5000 ppm by weight.
The process according to the invention can be applied in particular if high desulphurization rates of the gasoline are required, i.e. if the desulphurized gasoline must contain at most 10% of the sulphur present in the initial gasoline and optionally at most 5% or even at most 2% of the sulphur present in the initial gasoline, which corresponds to desulphurization rates in excess of 90% or even higher than 95 or 98%.
The process according to the invention comprises at least the following steps:
a1) at least one step, which consists in feeding the feedstock, preferably comprising the whole gasoline cut, across a catalyst enabling the diolefins and acetylenic compounds in the gasoline to be selectively hydrogenated without hydrogenating the olefins,
a2) optionally, at least one optional step which consists in feeding at least part of the initial gasoline or the gasoline hydrogenated at step a1, preferably all of the initial or hydrogenated gasoline from step a1, across a catalyst enabling at least part of the light sulphur compounds (for example: ethyl mercaptan, propyl mercaptan, thiophen) to be transformed, together with at least a part of the diolefins or olefins, into heavier sulphur compounds. This step is preferably operated simultaneously with step a1, for example by feeding the initial gasoline across a catalyst that is capable of both hydrogenating the diolefins and acetylenics and of converting the light sulphur compounds and a part of the diolefins or olefins into heavier sulphur compounds, or across a separate catalyst but one which enable this transformation to occur in the same reactor as that used for step a1. Optionally, with certain types of feedstock, an increase in the mercaptan content after a1) or a2) may possibly be observed, this increase in the mercaptan content probably being due to hydrogenolysis of disulphides with a high molecular weight. During this step, all of the light sulphur compounds, i.e. the compounds whose boiling point is lower than that of thiophen, may be transformed. Of these compounds, mention may be made of CS2, dimethyl sulphide, methylethyl sulphide or COS.
b) at least one step with a view to separating the initial gasoline into at least a light gasoline (light fraction), at least one intermediate gasoline (intermediate fraction) and a heavy gasoline (heavy fraction). The cut point of the light gasoline is determined with a view to limiting the sulphur content of the light gasoline and enabling it to be used in the gasoline pool, preferably without any additional treatment, in particular without desulphurization. The cut point of the intermediate gasoline is generally determined by the restrictions imposed by the reforming process in which the latter will be treated. One of the preferred configurations is to fractionate the gasoline in order to obtain a light fraction, a heavy fraction and two intermediate gasolines: a first intermediate gasoline mainly consisting of compounds with six carbon atoms, which is then preferably mixed with the heavy fraction of gasoline, preferably prior to step c1 or optionally between the saturation treatment of unsaturated sulphur compounds (step c1) and the decomposition of these compounds (step c2), and a second intermediate gasoline mainly comprising molecules having 7 or 8 carbon atoms (C7 or C8) which is treated at step d.
c1) at least one step, which consists in treating at least a part of the heavy gasoline and optionally at least a part of the intermediate cuts on a catalyst enabling at least some of the unsaturated sulphur compounds present in said feedstock, such as the thiophen compounds for example, to be converted into saturated sulphur compounds such as thiophanes (or thiacyclopentane) or mercaptans for example, in a series of reactions as described below: 
It is also possible to operate a total decomposition reaction during which H2S is released, generally accompanied by significant saturation reactions of the unsaturated sulphur compounds.
This hydrogenation reaction may be operated on any catalyst conducive to these reactions such as a catalyst containing at least one metal from Group VIII and/or at least one metal from group VIb, preferably at least partially in the form of sulphides. When using such a catalyst, the operating conditions are adjusted so that at least some of the unsaturated compounds, such as the thiophen compounds, can be hydrogenated whilst limiting hydrogenation of the olefins.
c2) following this treatment, at least one step c2 may be operated, in which the saturated sulphur compounds present in the initial gasoline or obtained after the saturation reaction (step c1) are converted into H2S by the reactions given as examples below: 
This treatment may be operated on any catalyst enabling the saturated sulphur compounds (mainly compounds of the thiophane type or mercaptan type) to be converted. For example, the catalyst used may have a base of at least one metal from group VIII of the old periodic table (groups 8, 9 or 10 of the new periodic table).
The heavy gasoline thus desulphurized is then optionally stripped (i.e. a gaseous flow, preferably containing an inert gas or gases, is fed through this gasoline) in order to remove the H2S produced during the hydro-desulphurization process. The light gasoline separated at step b and the heavy gasoline desulphurized at step c1 and/or at step c2 may then optionally either be mixed and fed into the gasoline pool of the refinery or treated separately without being mixed.
d) treatment of at least one of the intermediate cuts by a process intended to remove virtually all of the sulphur and nitrogen compounds from this fraction and preferably to hydrogenate all of the olefins, after which the effluent thus hydro-treated is treated on a reforming catalyst to enable the paraffins to be isomerized and dehydrocyclized.
e) optionally a step e at which at least two fractions are mixed, one of which, at least, having been subjected to a desulphurization treatment at step c1 and optionally c2 and/or at step d.
The different steps of the process according to the invention will be described in more detail below.
Hydrogenation of the Diolefins and Acetylenics (Step a1):
The step of hydrogenating the dienes enables almost all the dienes present in the gasoline cut containing the sulphur to be treated to be removed prior to hydro-desulphurization. It preferably takes place during the first step (step a1) of the process proposed by the invention, generally in the presence of a catalyst containing at least one metal from group VIII, preferably selected from the group consisting of platinum, palladium and nickel, and a substrate. For example, the catalyst used will have a base of nickel or palladium deposited on an inert substrate such as alumina or silica, for example, or a substrate containing at least 50% alumina.
The pressure applied is sufficient to maintain more than 60%, preferably 80% and a more preferably 95% by weight of the gasoline to be treated in liquid phase inside the reactor; generally speaking, it is between approximately 0.4 and approximately 5 MPa and preferably higher than 1 MPa and even more preferably between 1 and 4 MPa. The spatial velocity per hour of the liquid to be treated is between approximately 1 and approximately 20 hxe2x88x921 (feedstock volume per catalyst volume per hour), preferably between 3 and 10 hxe2x88x921 and more preferably between 4 and 8 hxe2x88x921. The temperature is more generally between approximately 50 and approximately 250xc2x0 C. and preferably between 80 and 230xc2x0 C. and more preferably between 150 and 200xc2x0 C., so as to guarantee sufficient conversion of the olefins. By very particular preference, it is limited to at most 180xc2x0 C. The hydrogen to feedstock ratio expressed in litres is generally between 5 and 50 litres per litre, preferably between 8 and 30 litres per litre.
The choice of operating conditions is of particular importance. More generally, operation is at a pressure and in the presence of a quantity of hydrogen slightly in excess of the stoichiometric value needed to hydrogenate the diolefins and acetylenics. The hydrogen and the feedstock to be treated are injected as ascending or descending flows into a reactor which preferably contains a fixed bed of catalyst.
Another metal may be used with the main metal to form a bimetallic catalyst, such as molybdenum or tungsten for example. The use of such catalytic formulas was claimed in patent FR 2 764 299, for example.
Gasoline from catalytic cracking may contain up to a few % by weight of diolefins. After hydrogenation, the diolefin content is generally reduced to less than 3000 ppm, even less than 2500 ppm and more preferably less than 1500 ppm. In certain cases, less than 500 ppm may be obtained. The diene content after selective hydrogenation maybe reduced to less than 250 ppm if necessary.
In one particular embodiment of the process according to the invention, the step of hydrogenating the dienes takes place in a hydrogenation catalytic reactor which has a catalytic reaction zone through which the entire feedstock is fed together with the quantity of hydrogen needed to induce the desired reactions.
Transformation of Light Sulphur Compounds into Heavier Compounds (Step a2):
This optional step consists in transforming the light sulphur compounds which would be found in the light gasoline at the end of separation step b if this step were omitted. It is preferably operated on a catalyst containing at least one element from group VIII (groups 8, 9 and 10 of the new periodic table) or containing a resin. In the presence of this catalyst, the light sulphur compounds are converted into heavier sulphur compounds, entrained in the heavy gasoline.
This optional step may be operated simultaneously with step a1. For example, it may be of particular advantage to operate, during hydrogenation of the diolefins and acetylenics, under conditions such that at least a part of the compounds present in the form of mercaptans are converted. Accordingly, the mercaptan content will be reduced to a certain degree. The hydrogenation procedure used for dienes described in patent application EP-A-0 832 958 maybe used for this purpose, which advantageously uses a catalyst with a palladium base, or that described in patent FR 2 720 754.
Another option is to use a catalyst with a nickel base identical to or different from the catalyst used in step a1, such as the catalyst recommended in the process described in patent U.S. Pat. No. 3,691,066, for example, which enables mercaptans (butyl mercaptan) to be converted into heavier sulphur compounds (methyl thiophen).
Another possible way of operating this step is to hydrogenate at least some of the thiophen to produce thiophane, which has a higher boiling point than thiophen (boiling point of 121xc2x0 C.). This step may be operated using a catalyst with a nickel, platinum or palladium base. This being the case, the temperatures will generally be between 100 and 300xc2x0 C. and preferably between 150 and 250xc2x0 C. The H2feedstock ratio is adjusted to between 1 and 20 litres per litre, preferably between 2 and 15 litres per litre, to permit the desired hydrogenation of the thiophenic compounds whilst minimising hydrogenation of the olefins present in the feedstock. The spatial velocity is generally between 1 and 10 hxe2x88x921, preferably between 2 and 4 hxe2x88x921 and the pressure between 0.5 and 5 MPa, preferably between 1 and 3 MPa. During this step, regardless of which process is used, some of the light sulphur compounds such as the sulphides (dimethyl sulphide, methylethyl sulphide), CS2 and COS may also be converted.
Another possible way of operating this step is to feed the gasoline across a catalyst having an acid function which will induce an addition reaction of the sulphur compounds present as mercaptans on the olefins and cause alkylation of the thiophen by these same olefins. For example, the gasoline to be treated may be fed through an ion-exchanger resin such as a sulphonic resin. The operating conditions will be adjusted to bring about the desired transformation whilst limiting parasitic oligomerization reactions by the olefins. Operation is generally in the presence of a liquid phase at a temperature ranging between 10 and 150xc2x0 C. and preferably between 10 and 70xc2x0 C. The operating pressure ranges between 0.1 and 2 MPa and preferably between 0.5 and 1 MPa. The spatial velocity is generally between 0.5 and 10 hxe2x88x921 and preferably between 0.5 and 5 hxe2x88x921. During this step, the conversion rate of the mercaptans is generally in excess of 50% and the conversion rate of the thiophen is generally in excess of 20%.
In order to minimise the oligomerization action of the acid catalyst optionally used, a known compound may be added to the gasoline to inhibit the oligomerizing action of the acid catalysts, such as alcohols, ethers or water for example.
Separation of the Gasoline into at Least Three Fractions (Step b):
During this step, the gasoline is fractionated into at least three fractions:
a light fraction with a residual sulphur content preferably limited to 50 ppm, more preferably limited to 25 ppm and even more preferably limited to 10 ppm, preferably enabling this cut to be used without any further treatment to reduce its sulphur content,
at least one intermediate fraction with a relatively low content of olefins and aromatics,
a heavy fraction in which the greater part of the sulphur initially present in the feedstock is concentrated.
This separation is preferably operated using a conventional distillation column, also known as a splitter. This fractionation column must be capable of splitting off from the gasoline a light fraction containing a small fraction of the sulphur, at least one intermediate fraction mainly consisting of compounds with 6 to 8 carbon atoms and a heavy fraction containing the greater part of the sulphur initially present in the initial gasoline.
This column generally operates at a pressure ranging between 0.1 and 2 MPa and preferably between 0.2 and 1 MPa. The number of theoretical plates of this separating column is generally between 10 and 100 and preferably between 20 and 60. The reflux rate of the column, expressed as the ratio between the liquid flow rate in the column and the feedstock flow rate, is generally less than one unit and preferably less than 0.8, these flow rates being measured in kilograms per hour (kg/h).
The light gasoline obtained after separation generally contains at least all the C5 olefins, preferably all the C5 compounds, and at least 20% of the C6 olefins. Generally speaking, this light fraction has a low sulphur content (less than 50 ppm for example), i.e. it is not generally necessary to treat the light fraction prior to using it as a fuel. However, in certain extreme cases, it might be conceivable to treat the light gasoline by softening
Hydrogenation of the Unsaturated Sulphur Compounds (Step c1):
This step is applied to the heavy gasoline optionally mixed with a least a part of an intermediate fraction obtained after the separation step b. By preference, this intermediate fraction essentially consists (i.e. more than 60% by weight, preferably more than 80% by weight) of C6 or C7 molecules and the greater part of the sulphur compounds with a boiling point close to that of the azeotrope of the thiophen with paraffins, give or take approximately 20%. This step consists in converting at least some of the unsaturated sulphur compounds, such as the thiophenic compounds, into saturated compounds, for example into thiophanes (or thiacyclopentanes) or mercaptans or alternatively optionally hydrogenolyzing these unsaturated sulphur compounds, at least partially, to form H2S.
This step may be operated, for example, by feeding the heavy fraction, optionally mixed with at least some of an intermediate fraction, through a catalyst containing at least one element from group VIII and/or at least one element from group VIb at least partially in sulphide form, in the presence of hydrogen, at a temperature ranging between approximately 200xc2x0 C. and approximately 350xc2x0 C., preferably between 220xc2x0 C. and 290xc2x0 C., at a pressure generally ranging between 1 and approximately 4 MPa, preferably between 1.5 and 3 MPa. The spatial velocity of the liquid ranges between approximately 1 and approximately 20 hxe2x88x921 (expressed as liquid volume per catalyst volume and per hour), preferably between 1 and 10 hxe2x88x921, more especially preferably between 3 and 8 hxe2x88x921. The H2/HC ratio is between 50 and 600 litres per litre and preferably between 300 and 600 litres per litre.
To hydrogenate the unsaturated sulphur compounds in the gasoline, at least partially, using the process according to the invention, at least one catalyst is generally used, containing at least one element from group VIII (metals from groups 8, 9 and 10 of the new periodic table, i.e. iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum) and/or at least one element from group VIb (metals from group 6 of the new periodic table, i.e. chromium, molybdenum or tungsten), on an appropriate substrate.
The content of metal from group VIII expressed as an oxide is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight. The content of metal from group VIb is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight.
If one is used, the element from group VIII is preferably cobalt and the element from group VIb, if one is used, is generally molybdenum or tungsten. Combinations such as cobalt-molybdenum are preferred. The catalyst substrate is usually a porous solid such as an alumina, a silica-alumina or other porous solids, for example, such as magnesia, silica or titanium oxide, alone or mixed with alumina or silica-alumina. In order to reduce hydrogenation of the olefins present in the heavy gasoline to a minimum, it is of advantage to use by preference a catalyst in which the density of molybdenum, expressed as a % by weight of MoO3 per unit of surface area is greater than 0.07 and preferably greater than 0.10. The catalyst proposed by the present invention preferably has a specific surface area of less than 190 m2/g, more preferably less than 180 m2/g, and more especially preferably less than 150 m2/g.
After introducing the element or elements and optionally shaping the catalyst (if this step is operated with a mixture which already contains the base elements), the catalyst is activated in an initial step. This activation may be effected either by oxidation followed by reduction or by direct reduction or by calcination only. The calcination step is generally operated at temperatures ranging from approximately 100 to approximately 600xc2x0 C. and preferably ranging between 200 and 450xc2x0 C., with an air flow. The reduction step is operated under conditions that will enable at least some of the oxidised forms of the metal from group VIII and/or the metal from group VIb to be converted to the metallic state. Generally speaking, it consists in treating the catalyst in a flow of hydrogen at a temperature of preferably less than or equal to 300xc2x0 C. The reduction may be effected, at least partly, by means of chemical reducers.
The catalyst is preferably used, at least partially, in its sulphide form. The sulphur may be introduced before or after any activation step, i.e. calcination or reduction. By preference, no oxidation step is effected until the sulphur or a sulphur compound has been introduced onto the catalyst.
Accordingly, if sulphur is added to the catalyst after drying, for example, it is preferable not to calcine the catalyst whereas a reduction step may optionally be run after sulphurization.
The sulphur or a sulphur compound may be introduced ex situ, i.e. externally to the reactor in which the process according to the invention takes place, or m situ, i.e. inside the reactor used for the process according to the invention. In the latter case, the catalyst is preferably reduced under the conditions described above before adding sulphur by feeding in a feedstock containing at least one sulphur compound which, once decomposed, will cause sulphur to fix on the catalyst. This feedstock may be gaseous or liquid, for example hydrogen containing H2S or a liquid containing at least one sulphur compound.
By preference, the sulphur compound is added to the catalyst ex situ. For example, after the calcination step, a sulphur compound may be introduced onto the catalyst, optionally in the presence of another compound. The catalyst is then dried before being transferred to the reactor used to implement the process according to the invention. In this reactor, the catalyst is then treated with hydrogen in order to transform at least some of the main metal into sulphide. A procedure which is particularly well suited to the invention is that described in patents FR-B-2 708 596 and FR-B-2 708 597.
During the process of the invention, the conversion rate of unsaturated sulphur compounds is higher than 15% and preferably in excess of 50%. At the same time, the hydrogenation rate of the olefins is preferably less than 50%, more preferably less than 40% and even more preferably less than 35% during this step.
During the process of the invention, the gasoline treated during step c1 may optionally contain at least some of at least one intermediate fraction obtained during step b. For example, it may be of advantage during this step to treat a fraction of the gasoline which will not be fed to the catalytic reforming process.
The effluent resulting from this first hydrogenation step is then optionally directed to step c2, which enables the saturated sulphur compounds to be decomposed to produce H2S.
Decomposition of the Saturated Sulphur Compounds (Step c2):
The feedstock at this stage consists either of the effluent issuing from step c1 only or a mixture comprising the effluent from step c1 and at least some of at least one intermediate fraction. By preference, this intermediate fraction essentially (i.e. more than 60% by weight, preferably more than 80% by weight) consists of C6 or C7 molecules as well as the greater part of the sulphur compounds with a boiling point close to that of the azeotrope of thiophen with the hydrocarbons, give or take 20%.
During this step, the saturated sulphur compounds are transformed in the presence of hydrogen on an appropriate catalyst. The unsaturated compounds that were not hydrogenated during step c1 may also be decomposed simultaneously. This transformation takes place without significantly hydrogenating the olefins, i.e. during this step, the quantity of hydrogenated olefins is generally limited to less than 20% by volume relative to the olefins contained in the initial gasoline and preferably limited to 10% by volume relative to the olefins contained in the initial gasoline.
Catalysts which might be suitable for this step of the process according to the invention, although this list is not restrictive, are catalysts which generally contain at least one base element (metal) selected from the group VIII elements and preferably selected from the group consisting of nickel, cobalt, iron, molybdenum, tungsten. These metals may be used alone or in combination, are preferably applied to a substrate and are used in their sulphide form. It is also possible to add at least one promoter to these metals, for example tin. By preference, the catalysts used will contain nickel or nickel and tin or nickel and iron or cobalt and iron or alternatively cobalt and tungsten. Said catalysts are more preferably sulphurized and are very preferably pre-sulphurized in situ or ex situ. The catalyst used for step c2 is preferably of a different nature and/or composition from that used for step c1.
The content of base metal in the catalyst used for the process according to the invention generally ranges between approximately 1 and approximately 60% by weight, preferably between 5 and 20% by weight and even more preferably between 5 and 9%. By preference, the catalyst is generally shaped, preferably in the form of beads, pellets, of extruded for example as trilobes. The metal may be incorporated in the catalyst by depositing it on the pre-formed substrate and may also be mixed with the substrate prior to the shaping step. The metal is generally introduced in the form of a precursor salt, generally soluble in water, such as nitrates, heptamolybdates, for example. This process of introduction is not specific to the invention. Any other process of introduction known to the person skilled in the art may be used.
The catalyst substrates used in this step of the process according to the invention are generally porous solids selected from the refractory oxides such as alumina, silica and silica-alumina, magnesia, for example, as well as titanium oxide and zinc oxide, it being possible to use these latter oxides alone or mixed with alumina or silica-alumina By preference, the substrates are transition alumina or silica with a specific surface area ranging between 25 and 350 m2/g. Natural compounds such as diatomaceous earth or kaolin may also be suitable substrates for the catalysts used for this step of the process.
In a preferred mode of preparing the catalyst, after at least one metal or precursor of said metal has been introduced and the catalyst optionally shaped, the catalyst is activated in a first step. This activation may be effected either by oxidation followed by reduction or by reduction after drying without calcination, or alternatively by calcination only. If calcination is used, the temperatures generally range from approximately 100xc2x0 C. to approximately 600xc2x0 C. and preferably range between 200xc2x0 C. and 450xc2x0 C., with a flow of air. The reduction step is operated under conditions that will enable at least some of the oxidised form s of the base metal to be converted to the metallic state. Generally speaking, it consists of treating the catalyst under a flow of hydrogen at a temperature at least equal to 300xc2x0 C. The reduction may also be at least partially operated using chemical reducers.
The catalyst is preferably used, at least partially, in its sulphurized form, which has the advantage of limiting to a maximum any risk of hydrogenation of the unsaturated compounds such as olefins or aromatic compounds during the start-up phase. The sulphur may be introduced between different activation steps. By preference, no oxidation step is operated until the sulphur or a sulphur compound has been introduced onto the catalyst. The sulphur or a sulphur compound may be introduced ex situ, i.e. externally to the reactor in which the process according to the invention takes place, or in situ, i.e. inside the reactor used for the process according to the invention. In the latter case, the catalyst is preferably reduced under the conditions described above before adding sulphur by feeding in a feedstock containing at least one sulphur compound which, once decomposed, will cause sulphur to fix on the catalyst. This feedstock may be gaseous or liquid, for example hydrogen containing H2S or a liquid containing at least one sulphur compound.
By preference, the sulphur compound is added to the catalyst ex situ. For example, after the calcination step, a sulphur compound may be introduced onto the catalyst, optionally in the presence of another compound. The catalyst is then dried before being transferred to the reactor used to implement the process according to the invention. In this reactor, the catalyst is then treated with hydrogen in order to transform at least some of the base metal and optionally another metal into sulphide. A procedure which is particularly well suited to the invention is that described in patents FR-B-2 708 596 and FR-B-2 708 597.
After sulphurization, the sulphur content of the catalyst is generally between 0.5 and 25% by weight, preferably between 4 and 20% by weight and even more preferably between 4 and 10% by weight. The purpose of the hydro-sulphurization process operated during this step c2 is to convert to H2S the saturated sulphur compounds of the gasoline which were subjected to at least one hydrogenation process before the unsaturated sulphur compounds during step c1. This enables an effluent to be obtained which meets the desired specifications in terms of content of sulphur compounds. The resultant gasoline undergoes only a slight loss of octane (drop in the Research and/or Motor Octane Number).
The treatment intended to decompose the saturated sulphur compounds after step c1 of the process is operated in the presence of hydrogen with a catalyst containing at least one base metal selected from the group consisting of nickel, cobalt, iron, molybdenum and tungsten, used alone or mixed with one another, at a temperature ranging between approximately 100xc2x0 C. and approximately 400xc2x0 C., preferably between approximately 150xc2x0 C. and approximately 380xc2x0 C., more especially preferably between 210xc2x0 C. and 360xc2x0 C. and most preferably between 220xc2x0 C. and 350xc2x0 and a pressure generally ranging by preference between approximately 0.5 and approximately 5 MPa, preferably between 1 and 3 MPa, more preferably between 1.5 and 3 MPa. The spatial velocity of the liquid ranges between approximately 0.5 and approximately 10 hxe2x88x921 (expressed as liquid volume per catalyst volume per hour), preferably between 1 and 8 hxe2x88x921. The H2/HC ratio is adjusted to the desired hydro-desulphurization rates within the range of between approximately 100 and approximately 600 litres per litre, preferably between 20 and 300 litres per litre. All or some of this hydrogen may optionally be drawn from step c1 (unconverted hydrogen) or may be unconsumed hydrogen recycled from steps a1, a2, c2 or d.
It has been found that using this second catalyst for this step, under specific operating conditions, enables the saturated compounds contained in the effluent issuing from step c1 to be decomposed into H2S. This approach enables a high global level of desulphurization to be obtained at the end of all the steps of the process according to the invention whilst minimising the octane loss resulting from saturation of the olefins because the olefin conversion during step c1 is generally limited to at most 20% by volume of the olefins, preferably at most 10% by volume.
Hydro-Treatment of at Least One Intermediate Cut (Step d):
This treatment of at least one of the intermediate cuts is intended to eliminate virtually all the sulphur and nitrogen compounds from this fraction and to treat the effluent hydro-treated in this manner on a reforming catalyst to enable the paraffins to be isomerized and dehydrocyclized. This step is applied to at least a part of an intermediate fraction obtained from step b.
It consists in treating said fraction on a catalyst or on a series of catalysts, i.e. obtaining a fraction with a content of sulphur and nitrogen that is preferably less than 5 ppm and more preferably less than 1 ppm by weight by converting the sulphur or nitrogen compounds into H2S and ammonia respectively.
This step is generally operated by feeding the fraction through at least one conventional hydro-treatment catalyst under conditions that will enable sulphur and nitrogen to be eliminated. Particularly suitable catalysts are, for example, catalysts with a base of a metal from group VIII such as cobalt or nickel and a metal from group VI such as tungsten or molybdenum. Typically, although these conditions are not restrictive, this treatment may be operated on a catalyst of the HR 306 or HR 448 type sold by Procatalyse, at a temperature generally ranging between 250 and 350xc2x0 C., an operating pressure generally ranging between 1 and 5 MPa, preferably between 2 and 4 MPa, and a spatial velocity generally ranging between 2 and 8 hxe2x88x921 (expressed as volume of liquid feedstock per catalyst volume per hour). During this treatment, almost all of the olefins present in this fraction are hydrogenated.
The resultant effluent is cooled and the decomposition products are then separated using any technique known to the person skilled in the art. Conceivable processes would be washing, stripping or alternatively extraction, for example.
The effluent corresponding to one of the intermediate fractions from which the sulphur and nitrogen have been removed is then treated on a catalyst or a series of catalysts to enable said fraction to reform, i.e. to bring about at least partial dehydrogenation of the saturated cyclic compounds, isomerize the paraffins and dehydrocyclize the paraffins present in the intermediate fraction treated. This treatment is intended to increase the octane number of the respective fraction. This process is operated using a conventional catalytic reforming process. It may be of advantage to use xe2x80x9cfixed bedxe2x80x9d or xe2x80x9cfluidized bedxe2x80x9d processes for this purpose, in which the catalyst is disposed respectively in a fixed or alternatively fluidized bed and optionally circulated through at least one reactor and through an external circulation loop optionally incorporating other reactors and/or at least one re-generator. During implementation of the process, the desulphurized effluent is brought into contact with a reforming catalyst, generally having a platinum base on an alumina substrate, at a temperature ranging between 400xc2x0 C. and 700xc2x0 C. at an hourly spatial velocity (kg of treated feedstock per hour and per kg of catalyst) ranging between 0.1 and 10. The operating pressure may range between 0.1 and 4 MPa. Some of the hydrogen produced during the different reactions may be recycled in a ratio of between 0.1 and 10 moles of hydrogen per mole of feedstock.
FIG. 1 illustrates an example of one embodiment of the process according to the invention. In this example, a gasoline cut (initial gasoline) containing sulphur is introduced via line 1 into a catalytic hydrogenation reactor 2, which enables the diolefins and/or the acetylenic compounds present in said gasoline cut to be selectively hydrogenated (step a1 of the process). The effluent 3 from the hydrogenation reactor is fed into a reactor 4, which contains a catalyst capable of converting the light sulphur compounds together with the diolefins or olefins into heavier sulphur compounds (step a2). The effluent 5 from the reactor 4 is then fed to the fractionation column 6 enabling the gasoline to be separated into 3 fractions (step b).
The first fraction obtained is a light fraction 7. This light cut preferably contains less than 50 ppm of sulphur and does not need to be desulphurized because the light sulphur compounds present in the initial gasoline were converted into heavier compounds during step a2.
A second fraction 8 (intermediate fraction) is obtained, which is firstly fed to a catalytic desulphurization reactor 10 and then via line 11 to a catalytic reforming reactor (step d).
A third fraction (heavy fraction) is obtained via line 9. This cut is firstly treated in a reactor 14 on a catalyst that will enable at least some of the unsaturated sulphur compounds present in the feedstock to be converted into saturated sulphur compounds (step c1). The effluent 15 from the reactor 14 is fed to the reactor 16 (step c2) which contains a catalyst to promote decomposition of the saturated sulphur compounds initially present in the feedstock and/or formed in the reactor 14 into H2S.
The light cut 7 as well as the effluent 13 (from the reforming reactor 14) and the effluent 17 (from the decomposition reactor 13) are mixed to form the desulphurized gasoline 18 (step e).
Using other, preferred implementing processes, illustrated in FIG. 1, it is also possible to direct at least a part of the intermediate fraction that was not desulphurized (line 8) either via line 19 and then mixed with the heavy fraction 9 to the reactor 14 (step c1) or via line 20 and then mixed with the effluent 15 to the reactor 16 (step c2).
The invention is illustrated by the examples below.